无机材料学报 ›› 2023, Vol. 38 ›› Issue (12): 1466-1474.DOI: 10.15541/jim20230215
所属专题: 【能源环境】锂离子电池(202312)
收稿日期:
2023-05-05
修回日期:
2023-06-25
出版日期:
2023-07-28
网络出版日期:
2023-07-28
通讯作者:
万 勇, 教授. E-mail: wanyongqd@hotmail.com;作者简介:
谭淑雨(1998-), 女, 硕士研究生. E-mail: tsy1576362772@163.com
TAN Shuyu(), LIU Xiaoning, BI Zhijie, WAN Yong(
), GUO Xiangxin(
)
Received:
2023-05-05
Revised:
2023-06-25
Published:
2023-07-28
Online:
2023-07-28
Contact:
WAN Yong, professor. E-mail: wanyongqd@hotmail.com;About author:
TAN Shuyu (1998-), female, Master candidate. E-mail: tsy1576362772@163.com
Supported by:
摘要:
聚氧化乙烯(PEO)基固体电解质具有成本低、对锂稳定、易于大规模生产等优点, 是固态锂电池最有前途的固体电解质。然而, PEO对高压正极不稳定, 严重限制了其在高能量密度领域的应用。本研究在LiNi0.6Co0.2Mn0.2O2 (NCM)正极颗粒上部分包覆环化聚丙烯腈(cPAN)纳米层作为电子导电层, 在NCM/PEO界面上引入离子液体作为离子导电通道, 用以提高PEO与高压NCM正极的相容性。其中, cPAN层不仅在物理上隔离了PEO电解质与NCM正极的直接接触, 而且cPAN中具有非局域的sp2 π键, 有助于正极内部的电子传输。同时, 高离子电导率的离子液体的流动性较高, 可以充分润湿正极侧界面, 并在循环过程中分解为富LiF和Li3N的CEI层, 进一步限制PEO电解质的氧化分解。基于上述复合策略的固态NCM/Li电池可在0.1C (1C=0.18 A·g-1), 4.30 V截止电压下稳定循环100次, 且容量保持率可达85.3%。本研究通过表面包覆和界面修饰, 为提高PEO基电解质对高压正极的稳定性提供了可行方案。
中图分类号:
谭淑雨, 刘晓宁, 毕志杰, 万勇, 郭向欣. 正极包覆与界面修饰: 双策略改善聚氧化乙烯固态电解质对高电压正极稳定性[J]. 无机材料学报, 2023, 38(12): 1466-1474.
TAN Shuyu, LIU Xiaoning, BI Zhijie, WAN Yong, GUO Xiangxin. Jointing of Cathode Coating and Interface Modification for Stabilizing Poly(ethylene oxide) Electrolytes Against High-voltage Cathodes[J]. Journal of Inorganic Materials, 2023, 38(12): 1466-1474.
Fig. 1 (a) Preparation process of NCM@cPAN powder, (b) schematic representation of as-prepared NCM@cPAN particle, and (c) schematic diagram of the solid-state NCM@cPAN+IL/PEO/Li cell
Fig. 2 (a) FT-IR spectra of pristine PAN and PAN treated at 400 ℃, (b) schematic diagrams of pristine PAN and cPAN, and (c) Raman spectra of PAN, cPAN, NCM, and NCM@cPAN
Fig. 3 (a) XRD patterns of NCM, NCM@PAN, and NCM@cPAN powders; SEM images of (b, c) NCM, (d, e) NCM@PAN, and (f, g) NCM@cPAN powders; (h, i) TEM images of NCM@cPAN; (j) EDS mappings of C, N, O, Mn, Co and Ni elements of the region in (f)
Fig. 4 Cycling performance of solid-state NCM@cPAN+IL/PEO/Li batteries Typical charge-discharge curves and the corresponding specific capacities with cutoff voltages of (a, d) 4.20 V, (b, e) 4.25 V, and (c, f) 4.30 V
Fig. 5 (a) Charge-discharge curves, and (b) corresponding specific capacities for solid-state NCM@cPAN+IL/PEO/Li batteries at various current densities; (c) Typical charge-discharge curves and (d) corresponding specific capacities and Coulombic efficiency for solid-state NCM@cPAN+IL/PEO/Li batteries with high cathode loading of ~6.2 mg·cm-2
Fig. 6 (a, c) F1s and (b, d) N1s XPS spectra of PP13-TFSI (a, b) before and (c, d) after cycling; (e) Schematic diagram of TFSI− decomposition during cycling
Fig. 7 (a) FT-IR spectra of PEO electrolyte before and after cycling; SEM images of NCM@cPAN cathodes (b) before and (c) after cycling; (d) Ni2p XPS spectra of NCM@cPAN cathode before and after cycling
Fig. S4 Rate performance of solid NCM@cPAN+IL/PEO/Li batteries at various current densities (a, c) Typical charge-discharge curves and (b, d) corresponding specific capacities with the cutoff voltages of (a, b) 4.25 V, and (c, d) 4.30 V
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